Semiconductor material and method for enhancing solubility of a dopant therein

ABSTRACT

A method for enhancing the equilibrium solubility of boron ad indium in silicon. The method involves first-principles quantum mechanical calculations to determine the temperature dependence of the equilibrium solubility of two important p-type dopants in silicon, namely boron and indium, under various strain conditions. The equilibrium thermodynamic solubility of size-mismatched impurities, such as boron and indium in silicon, can be raised significantly if the silicon substrate is strained appropriately. For example, for boron, a 1% compressive strain raises the equilibrium solubility by 100% at 1100° C.; and for indium, a 1% tensile strain at 1100° C., corresponds to an enhancement of the solubility by 200%.

This application is a divisional application of Ser. No. 10/246,890, nowU.S. Pat. No. 6,617,228, filed Sep. 18, 2002, which is continuation ofSer. No. 09/945,932, now U.S. Pat. No. 6,498,078, filed Sep. 4, 2001,which claims benefit of 60/230,615, filed Sep. 5, 2000.

The United States Government has rights in this invention pursuant toContract No. W-7405-ENG-48 between the United States Department ofEnergy and the University of California for the operation of LawrenceLivermore National Laboratory.

BACKGROUND OF THE INVENTION

The present invention relates to solubility of dopants in semiconductormaterials, particularly to enhancing the solubility, and moreparticularly to a method for enhancing solubility of boron and indium insilicon.

Ion implantation allows for exceptional control and reproducibility inthe introduction of dopants into the near-surface region ofsemiconductors. As a result, it has been the universal method of choicefor doping MOS transistors in silicon-based integrated circuits sincethe beginning of the semiconductor revolution. However, an undesirableeffect of ion-implantation is that it introduces significant damage intothe silicon wafer in the form of point defects and their clusters, Faheyet al Rev. Mod. Phys. 61, 289 (1989). For a device to be operationalthese defects must be removed and the dopants electrically activatedthrough high-temperature annealing. The annealing procedure leads tounwanted dopant diffusion, as well as nucleation and growth of dopantclusters and precipitates which results in incomplete activation.

Experience has shown that the solubility of boron in silicon undernon-equilibrium thermodynamic conditions prevailing during the annealingprocedure, i.e., in the presence of excess silicon self-interstitialatoms, is lower than its equilibrium thermodynamic value. The latterthus determines an upper bound for the concentration of substitutional Batoms in silicon. As technology continues to evolve toward smaller andfaster transistors, this limit may soon be reached unless new ideasand/or technologies are brought forward that can reduce dopant diffusionduring processing while at the same time increasing their electricalactivity, see Packan, Science 285, 2079 (1999).

The most widely used p-type dopant, i.e., boron, has a maximumsolubility of less than 1 at. % in silicon at the annealing temperatureof interest. This sets the limit for the highest concentration ofelectrically active boron impurities that can be reached with currentimplantation techniques. Already the next generation of transistors willbe dangerously close to this solubility limit. Another p-type dopantcandidate with excellent diffusion properties, i.e., indium, has beenused only on a small scale mainly because of its very low solubility insilicon. Thus, there is a need to remedy this acute problem faced by thesemiconductor industry.

The present invention provides a solution to the above-reference problemby a method for enhancing the solubility of boron and indium in silicon.The invention is based on the use of first-principles density-functionaltheory (DFT) in the local-density approximation (LDA) to calculate thetemperature dependence of the equilibrium solubility of boron and indiumin crystalline silicon under various strain conditions. Verification ofthis invention has shown that the equilibrium thermodynamic solubilityof significantly size-mismatched dopants in silicon, such as boron orindium, can be raised by more than 100% if the silicon substrate isstrained appropriately.

SUMMARY OF THE INVENTION

It is an object of the present invention to increase the solubility ofdopants in semiconductor substrate materials.

A further object of the invention is to provide a method for enhancingthe solubility of dopants in silicon.

Another object of the invention is to provide a method for enhancing thesolubility of boron and indium in silicon.

Another object of the invention is to utilize strain in a semiconductorsubstrate to increase solubility of dopants therein.

Another object of the invention is to induce tensile strain orcompression (bi-axials) strain under elevated temperatures forincreasing solubility of dopants in semiconductor materials, such assilicon.

Another object of the invention is to enhance the solubility of dopants,such as boron and indium, in silicon by at least 100% using a 1%compression or tensile strain at an elevated temperature.

Other objects and advantages of the present invention will becomeapparent from the following description and accompanying drawings.Basically the invention involves increase the solubility of dopants in asemiconductor material. More specifically the invention involves amethod for enhancing solubility of boron and indium in silicon. As aresult of the method of this invention the solubility of a dopant, suchas boron or indium, in a semiconductor material, such as silicon, isincreased by over 100%. This is accomplished by imposing a strain of thesemiconductor material under an elevated temperature. Thus, thisinvention greatly advances the state of the art of silicon processingfor manufacturing of integrated circuit devices, for example. It hasbeen determined by this invention that the equilibrium thermodynamicsolubility of size-mismatched impurities, such as boron and indium insilicon, can be raised significantly if the silicon substrate isstrained appropriately. For example, a 1% compression (bi-axial) strainof silicon raises the equilibrium solubility of boron in silicon by 100%at 1100° C., or 1% tensile strain of silicon at 1100° C. enhances thesolubility of indium in silicon by 200%.

BRIEF DESCRIPTION OF THE DRAWINGS

The accompanying drawings, which are incorporated into and form a partof the disclosure, illustrate the method of the invention and, togetherwith the description, serve to explain the principles of the invention.

FIG. 1 illustrates a compression strain induced in a silicon substrate.

FIG. 2 graphically illustrates the temperature dependence of boronsolubility in 1% strained silicon and unstrained silicon.

DETAILED DESCRIPTION OF THE INVENTION

The present invention involves increasing the solubility of dopants insemiconductor materials, particularly increasing the solubility of boronand indium in silicon. This is basically accomplished by placing astrain on the silicon at elevated temperatures. For example, it has beendemonstrated that a 1% compressive strain raises the equilibriumsolubility by 100% at 1100° C. for boron, and for indium a 1% tensilestrain at 1100° C. corresponds to an enhancement of solubility by 200%.This method for enhancing the solubility of boron and indium in siliconresulted from the performance of first-principles quantum mechanicalcalculation relative to the temperature dependence of the equilibriumsolubility of two important p-type dopants in silicon, namely boron andindium under various strain conditions. It was found that theequilibrium thermodynamic solubility of size-mismatched impurities, suchas boron and indium in silicon, can be raised significantly if thesilicon substrate is strained accordingly. The following partially setsforth theory basis, procedures, and data relative to the presentinvention.

The first-principles density-functional theory (DFT) [Phys. Rev. 136,B864 (1964)] in the local-density approximation (LDA) [Phys. Rev. 140,A1133 (1965)] was used to calculate the temperature dependence of theequilibrium solubility of B and In in crystalline Si under variousstrain conditions. We show that the equilibrium thermodynamic solubilityof size-mismatched dopants in silicon, such as B or In, can be raisedsignificantly if the Si substrate is strained appropriately. For boron,we demonstrate that a 1% compressive strain raises the equilibriumsolubility by 100% at 1100° C. For In, an equivalent tensile strain atthe same temperature corresponds to an enhancement of the solubility by200%.

The Si—B binary phase diagram shows that at 1200° C., the solidsolubility of B in Si is about 1 at. %. Beyond this concentration theexcess B atoms can form precipitates of a second phase, i.e., the SiB₃phase which is stable at 75 at. % B concentration. This phase has acomplicated structure based on distorted boron-rich icosohedralclusters, which suggests that SiB₃ precipitates formed in the two phaseregion of the Si—B phase diagram, are incoherent with the underlyingcubic diamond structure of the pure Si crystal. Under these conditionsone can derive the following expression for the maximum soluble Bconcentration in Si ([B]_(max)):[B]_(max)∝√n(T)exp(ΔH/(2k_(B)T)−E_(gap)/(4k_(B)T)).  (1)

Here n(T) is the intrinsic carrier concentration in Si, k_(B) is theBoltzmann constant, T is the temperature and E_(gap) is the electronicband-gap in Si. The enthalpy of solution (ΔH) is further derived to be:ΔH=4/3(E(SiB₃)−(E(Si))−(E(B⁻)−E _(F) −E(Si)),  (2)where E(SiB₃) and E(Si) denote the total energies per atom for the SiB₃and pure Si phases respectively. Furthermore E(B⁻) is the energy of anisolated negatively charged substitutional B impurity and E_(F) is theFermi level which depends on the temperature as well as the Bconcentration. Below we present our first-principles calculations forthese quantities and discuss their dependence upon strain.

In our calculations the unstrained Si crystal is represented by a cubicdiamond lattice grown along the (001) direction with a lattice constanta_(eq)=5.39 a.u., corresponding to the LDA prediction. A biaxial strainof x% is applied by changing the lattice constant of the {001} layers toa_({001)}=a_(eq)(1+0.01x) while choosing an interlayer spacing thatminimizes the total energy of the system (FIG. 1).

For the unstrained case we obtained an enthalpy of solution ΔH=0.762 eV.Experimentally, over the range 900° to 1325° C., B solubility shows anexponential dependence on temperature exp(−E/k_(B)T), where E=0.73±0.04eV. A similar fit of the theoretically derived temperature dependenceyields nearly perfect agreement, i.e., E=0.80 eV. These results areillustrated FIG. 2.

We find that compressive biaxial strain enhances the B solubility byreducing E_(gap) and increasing ΔH in Eq. 1. More precisely a onepercent compressive strain, i.e., a_({001})=0.99 a_(eq), leads to anincrease in ΔH of 0.1 eV and a decrease in E_(gap) of 0.11 eV. Theresulting B solubility is illustrated in Table 1, where it is comparedwith the unstrained case. Hence, we find that a 1% biaxial compressioncan raise [B]_(max) by more than 100% at 1100° C.

TABLE 1 (Boron Solubility Calculation) $\begin{matrix}{\lbrack B\rbrack = {{{Ae}^{\frac{\Delta G}{kT}}\quad{where}\quad{\Delta G}} = {{\Delta H} + {P\quad\Delta\quad V} - {T\quad\Delta\quad S}}}} \\{{\Delta H} = {{\frac{4}{3}\lbrack {{E( {B_{3}{Si}} )} - {E({Si})}} \rbrack} - \lbrack {{E( B^{-} )} - {E({Si})} - E_{F}} \rbrack}} \\{{\Delta E}_{F} \approx {{- {kT}}\quad{\ln( {\frac{\lbrack B\rbrack}{n_{i}(T)} + \frac{n_{i}(T)}{\lbrack B\rbrack}} )}}} \\{\lbrack B\rbrack \approx \sqrt{{Ae}^{\frac{\Delta s}{k}}e^{\frac{{\Delta H}_{0}}{kT}}e^{\frac{P\quad\Delta\quad V}{kT}}{{ni}(T)}}} \\{n_{i} \propto {T^{\frac{3}{2}}e^{- \frac{Eg}{2{kT}}}}}\end{matrix}\quad$

In practice, it can be problematic to prepare a strained Si wafer forion-implantation and subsequent annealing. One way is epitaxial growthon a slightly size-mismatched substrate with the same structure, i.e.,diamond structure. Silicon wafers are naturally produced with a goodamount of carbon contamination in them. However, the extremely lowsolubility of carbon in silicon results in polycrystalline substrateswhich renders them useless for this application. Zinc-Sulfite (ZnS) is amaterial with diamond structure and a lattice constant that is about0.4% smaller than Si. ZnS wafers can be produced cheaply and siliconthin films grown epitaxially on them, will accept a significantly higherconcentration of soluble boron dopants. Strains of the order of 0.4% canbe achieved by epitaxial growth of silicon on a ZnS substrate along(001) direction.

Using the same approach for In we find that a small expansive strain,i.e., for a_({001})>a_(eq), will lead to significant enhancement of itssolid solubility in Si. In particular we find that a 1% biaxial tensilestrain, i.e., a_({001})=1.01 a_(eq), increases ΔH by 0.15 eV and reducesE_(gap) by 0.17 eV (cf. Eq.1). These numbers correspond to an increasein In solubility in Si of about 200% at 1100° C. Hence we expect toreach much higher dopant concentrations if we ion-implant the In atomsinto a thin layer of Si, grown epitaxially on top of a Si₈₀—Ge₂₀ alloy.An even cheaper way would be to use an AIP substrate. This material isin diamond structure with a 0.6% larger lattice constant than silicon.

It has thus been shown that the present invention enables enhancing ofthe solubility of boron and indium in silicon by placing the siliconsubstrate under strain at an elevated temperature. By placing a siliconsubstrate at a 1% compressive (bi-axial) strain at 1100° C., equilibriumsolubility raises by 100%, and stains of the order of 0.4% can beachieved by epilaxial growth of silicon on a Zinc-Sulfite (ZnS)substrates along the (001) direction. By placing a silicon substrate ata 1% tensile strain at 1100° C., the enhancement of the solubility is200%, strains of this magnitude can be achieved by epitaxial growth ofsilicon on a Si₈₀—Ge₂₀ alloy substrate. Smaller strains of the order of0.6%o can be achieved cheaply by growing silicon on a Aluminum Phosphate(AIP) substrate along the (001) direction. This invention has clearapplication in silicon processing for the manufacture of integratedcircuit devices.

While particular embodiments of the invention along with particularmaterials and parameters have been described or illustrated to exemplifyand teach the principles of the invention, such are not intended to belimited. Modifications and changes may become apparent to those skilledin the art, and it is intended that the invention be limited only by thescope of the appended claims.

1. A semiconductor material having a equilibrium dopant solubility ofboron or indium of greater than 1% wherein said semiconductor materialcomprises silicon grown on a Aluminum Phosphate (AIP) substrate along a(001) direction.
 2. The semiconductor material of claim 1, wherein saidsilicon semiconductor material is p-type silicon comprising a dopant ofboron or indium.
 3. The semiconductor material of claim 2 wherein saiddopant includes boron and said semiconductor comprises SiB₃.